Abstract
Revised thermodynamic and dynamical properties of the hard sphere (HS) system are obtained from extensive molecular dynamics calculations carried out with large system sizes (number of particles, N) and long times. Accurate formulas for the compressibility factor of the HS solid and fluid branch are proposed, which represents the metastable region and takes into account its divergence at close packing. Some basic secondorder thermodynamic properties are obtained and a maximum in some of their derivatives in the metastable fluid region is found. The thermodynamic parameters associated with the meltingfreezing transition have been determined to four digit accuracy which generates accurate new values for the coexistence properties of the HS system. For the selfdiffusion coefficient, D, it is shown that relatively large systems (N > 104 ) are −1/3 required to achieve an accurate linear extrapolation of D to the infinite size limit with a D vs. Nplot. Moreover, it is found that there is a density dependence to the value of the slope in the linear regime. The density dependent correction becomes practically insignificant at higher densities and the hydrodynamic formula found in the literature is still accurate. However, with decreasing density the density dependence of the size correction cannot be neglected, which indicates that other sources of Ndependence, apart from those derived on purely hydrodynamic grounds, may also be important (and as yet unaccounted for). A detailed analytic representation of the density dependence of the HS selfdiffusion coefficient and the HS viscosity, η, is given. It is shown that the HS viscosity near freezing and in the metastable region can be described well by the KriegerDougherty equation. Both D and η start to scale at high densities and in the metastable region in such a way that Dη p = const, where p ' 0.97, and → 0 and η → ∞ at a packing fraction of 0.58 density which coincides with some previous predictions of the HS glass transition density.
Original language  English 

Pages (fromto)  68866899 
Number of pages  14 
Journal  Physical Chemistry Chemical Physics 
Volume  21 
Issue number  13 
Early online date  19 Mar 2019 
DOIs  
Publication status  Published  7 Apr 2019 
Keywords
 CRYSTALS
 EQUATIONOFSTATE
 FLUID
 FREEENERGY
 GEOMETRY
 LIQUIDS
 SELFDIFFUSION COEFFICIENT
 SIZE DEPENDENCE
 TRANSITION
 TRANSPORTCOEFFICIENTS
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Profiles

Marcus Campbell Bannerman
 Engineering, Engineering  Senior Lecturer
 Engineering (Research Theme)
 Centre for Energy Transition
Person: Staff, Academic